The topic of polymer nanocomposites remains an active area of research in the dielectrics community, due to the unique electrical properties that these materials could exhibit. To explain the behaviour of these materials, the importance of clarifying the interfaces between nanoparticles and polymer matrices has been emphasised. However,understanding of the interface in nanocomposites is unsatisfactory and, consequently,many experimental results remain unexplained. This thesis reports on an investigation into a polyethylene nanocomposite system that contains varying amounts of nanosilica that differ with respect to their surface chemistry. The addition of nanosilica, even with different surface chemistries, was found to enhance the nucleation density of polyethylene and perturb the spherulitic development. While less organised lamellar structures would be expected to lead to a lower breakdown strength, this does not appearto be the case for the material systems considered here under alternating current (AC) fields. In addition, nanosilica filled polyethylene was found to absorb significantly more water than unfilled polyethylene, with the consequence that both the permittivity and the loss tangent increase with increasing duration of water immersion. However, appropriate surface treatment of nanosilica reduces the water absorption effect and modifies the dielectric response of the nanocomposites compared with those containing an equivalent amount of untreated nanosilica. Although water absorption may not be a technologically desirable characteristic, the results indicate that water molecules can act as effective dielectric probes of interfacial factors. Meanwhile, the direct current (DC) breakdown strength reduces with the inclusion of increasing amount of nanosilica in the polyethylene, but surface treatment of nanosilica improves the DC breakdown strength with respect to equivalent nanocomposites containing untreated nanosilica. Results from space charge studies reveal increased space charge accumulation in the presence of the untreated nanosilica and, upon surface treatment of the nanosilica, the charge development was suppressed in comparison with nanocomposites containing an equivalent amount of untreated nanosilica. This observation suggests that space charge accumulation and DC failure are related in these systems and it would seem that control of surface chemistry is particularly critical in connection with the use of nanocomposites in DC applications. Finally, the mechanisms underpinning the concept of filler functionalisation in nanocomposites were investigated via the use of different aliphatic chain length silane coupling agents, and the results show that long silane chains enhance the DC breakdown strength of the resulting nanocomposites. The possible further enhancement in DC breakdown strength is also highlighted. Overall, this thesis demonstrates how a nanoparticle’s interface chemistry can affect both the structure and the electrical properties of the resulting nanocomposites, and serves as an important foundation towards the engineering of nanocomposites as the reliable electricalinsulation materials of the future, through the understanding of the interface.